CN115181038A - Carbodiimide modified isocyanate with long shelf life and preparation method and application thereof - Google Patents
Carbodiimide modified isocyanate with long shelf life and preparation method and application thereof Download PDFInfo
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- CN115181038A CN115181038A CN202210926663.0A CN202210926663A CN115181038A CN 115181038 A CN115181038 A CN 115181038A CN 202210926663 A CN202210926663 A CN 202210926663A CN 115181038 A CN115181038 A CN 115181038A
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- carbodiimide
- modified isocyanate
- isocyanate
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- 239000012948 isocyanate Substances 0.000 title claims abstract description 81
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 80
- 150000001718 carbodiimides Chemical class 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 18
- 239000011574 phosphorus Substances 0.000 claims abstract description 18
- 239000003426 co-catalyst Substances 0.000 claims abstract description 16
- 239000000853 adhesive Substances 0.000 claims abstract description 15
- 230000001070 adhesive effect Effects 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 238000009835 boiling Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 94
- 238000000034 method Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 10
- JDRJCBXXDRYVJC-UHFFFAOYSA-N OP(O)O.N.N.N Chemical compound OP(O)O.N.N.N JDRJCBXXDRYVJC-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 claims description 6
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 4
- 239000005819 Potassium phosphonate Substances 0.000 claims description 4
- PWAXUOGZOSVGBO-UHFFFAOYSA-N adipoyl chloride Chemical compound ClC(=O)CCCCC(Cl)=O PWAXUOGZOSVGBO-UHFFFAOYSA-N 0.000 claims description 4
- YXXXKCDYKKSZHL-UHFFFAOYSA-M dipotassium;dioxido(oxo)phosphanium Chemical compound [K+].[K+].[O-][P+]([O-])=O YXXXKCDYKKSZHL-UHFFFAOYSA-M 0.000 claims description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 4
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 claims description 4
- AUTOISGCBLBLBA-UHFFFAOYSA-N trizinc;diphosphite Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])[O-].[O-]P([O-])[O-] AUTOISGCBLBLBA-UHFFFAOYSA-N 0.000 claims description 4
- CWKYHZMWPLSOFA-UHFFFAOYSA-N 3-methyl-1-phenyl-2,5-dihydrophosphole Chemical compound C1C(C)=CCP1C1=CC=CC=C1 CWKYHZMWPLSOFA-UHFFFAOYSA-N 0.000 claims description 3
- UVECLJDRPFNRRQ-UHFFFAOYSA-N ethyl trifluoromethanesulfonate Chemical compound CCOS(=O)(=O)C(F)(F)F UVECLJDRPFNRRQ-UHFFFAOYSA-N 0.000 claims description 3
- GRJHONXDTNBDTC-UHFFFAOYSA-N phenyl trifluoromethanesulfonate Chemical compound FC(F)(F)S(=O)(=O)OC1=CC=CC=C1 GRJHONXDTNBDTC-UHFFFAOYSA-N 0.000 claims description 3
- MJYCCJGURLWLGE-UHFFFAOYSA-N propyl trifluoromethanesulfonate Chemical compound CCCOS(=O)(=O)C(F)(F)F MJYCCJGURLWLGE-UHFFFAOYSA-N 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 23
- 238000002425 crystallisation Methods 0.000 abstract description 7
- 230000008025 crystallization Effects 0.000 abstract description 7
- 230000002035 prolonged effect Effects 0.000 abstract description 6
- 238000006011 modification reaction Methods 0.000 abstract description 5
- 230000006872 improvement Effects 0.000 abstract description 4
- 238000010276 construction Methods 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 239000000539 dimer Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000007789 sealing Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 238000007599 discharging Methods 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- -1 coatings Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000011049 filling Methods 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- LFMAOMQWCSTELR-UHFFFAOYSA-N 2-methyl-2-oxo-1,2$l^{5}-oxaphospholan-5-one Chemical compound CP1(=O)CCC(=O)O1 LFMAOMQWCSTELR-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- GWLJTAJEHRYMCA-UHFFFAOYSA-N phospholane Chemical compound C1CCPC1 GWLJTAJEHRYMCA-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C267/00—Carbodiimides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses carbodiimide modified isocyanate with a long shelf life and a preparation method and application thereof. The preparation method comprises the following steps: 1) Mixing a phosphorus-containing reducing salt and a phosphorus heterocyclic catalyst in an inert low-boiling point solvent to obtain an activated co-catalyst solution; 2) Adding the co-catalyst solution into an isocyanate monomer containing 20-40% of 4, 4-diphenylmethane diisocyanate, 25-45% of 2, 4-diphenylmethane diisocyanate and 15-55% of 2, 2-diphenylmethane diisocyanate in mass ratio; 3) Removing the inert low-boiling-point solvent, and heating to 90-120 ℃ to carry out carbodiimide modification reaction. The carbodiimide modified isocyanate prepared by the invention has the advantages of prolonged product shelf life, low crystallization temperature, improvement of product storage and use conditions and reduction of product use limit. In addition, the adhesive prepared by the carbodiimide modified isocyanate has low construction viscosity and excellent low temperature resistance.
Description
Technical Field
The invention relates to modified isocyanate, in particular to carbodiimide modified isocyanate with a long shelf life and a preparation method and application thereof.
Background
Polyurethane materials are widely used for manufacturing polyurethane foams, coatings, adhesives, sealants and elastomers by virtue of excellent physical properties and machining properties of the polyurethane materials. 4, 4-diphenylmethane diisocyanate (4, 4-MDI) is one of important monomers for preparing polyurethane materials due to high reactivity, but the diisocyanate is solid at room temperature, and compared with the solid, liquid isocyanates are easier to transport and industrially feed. At present, the main storage, transportation and application modes of the monomer are 40-45 ℃ storage or the use of barreled solid MDI after high-temperature melting at 60-80 ℃, but dimers may grow rapidly in the process of high-temperature storage or material melting, so that the risk of solid precipitation or product performance influence is caused. In order to realize MDI liquefaction, carbodiimide (CDI) modification is carried out on isocyanate by main isocyanate suppliers such as Basf, hensman, dow, corsika, jinhu Tri-well, wanhua chemistry and the like, so as to realize isocyanate liquefaction, namely the liquefied MDI. Typical commercially available products include LUPRANATE MM103C, SUPRASEC @ 2020. ISONATE 143L, desmodur CD-C, coronate MX, WANNATE CDMDI-100L, and the like.
The carbodiimide modified product not only improves the storage and transportation characteristics of isocyanate, but also improves the performances of light resistance, flame resistance, hydrolysis resistance, initial strength increase and the like of an application product to a certain extent by utilizing the structure and chemical characteristics of CDI and UTI in the modified isocyanate because carbodiimide groups can carry out addition reaction with the isocyanate to form multi-functional Uretonimine (UTI).
Carbodiimide-modified isocyanates can be prepared by a variety of methods, but more generally by reacting isocyanates, such as 4,4-MDI, with an organophosphorus-based catalyst. The organophosphorus catalyst with more industrial application mainly comprises a low-efficiency catalyst phosphate compound and a high-efficiency catalyst phosphacycle compound. Wherein the reaction temperature of the phosphate catalyst is higher, generally 180-250 ℃, and the reaction lasts for 4-8 hours to ensure that the NCO content of the system reaches 29-30%; the reaction temperature of the phosphorus heterocyclic catalyst is relatively low, generally 90-120 ℃, and the reaction time is 2-8h to reach the same NCO value. The phosphacycle catalyst can quickly reach the reaction end point at a lower temperature, is favorable for reducing the self-polymerization reaction rate of isocyanate, reduces the initial dimer content of liquefied MDI, prolongs the time for reaching the saturated solubility of the dimer, and prolongs the shelf life.
However, in the method, the main composition of the liquefied MDI is still 4,4-MDI, the isocyanate group activity is higher, the isocyanate self-polymerization reaction also exists in the storage and industrial application processes, the growth speed of the dimer is rapidly accelerated along with the temperature rise, and the dimer precipitation risk is further increased when the dimer is stored under the high-temperature condition in summer. According to the technical specifications given by companies such as basf, hensman, dow, kesichu, jin lake three wells, and wanhua chemistry, the shelf life of liquefied MDI is only 6 months when stored at 20-30 ℃.
Currently, studies on liquefied MDI are mainly focused on improvement of appearance, stability, and low temperature resistance, and there are few technical documents on improvement of long-term storage stability.
CN113072465A discloses a method for preparing carbodiimide modified isocyanate by utilizing an organic metal compound and a phosphate ester catalyst system, which improves the low-temperature storage performance of carbodiimide isocyanate, but the process for preparing carbodiimide still has high-temperature reaction, the growth rate of dimer is higher, and the residual organic metal compound in the system is not subjected to inactivation treatment, so that isocyanate can be slowly catalyzed to be self-polymerized to generate dimer or trimer in the low-temperature storage process, the long-term storage stability of the product is influenced, and meanwhile, the reaction activity of isocyanate and polyol is also influenced to a certain extent.
CN112574068A discloses a method for preparing carbodiimide modified isocyanate with low color number and high stability, which is characterized in that the use amount of a catalyst is reduced and a terminator is added, so that the carbodiimide is not formed by further catalyzing the reaction of isocyanate groups in the storage process of a liquefied product at low/high temperature, carbon dioxide is released, and the risk of overpressure and viscosity increase of a container in the storage process of the product is reduced. However, the technical content does not relate to the solution of the dimer problem, and the shelf life of the product is still limited to 6 months.
Therefore, how to improve the storage shelf life of the liquefied MDI and widen the storage conditions is of great significance to improve the storage and processing conditions of downstream application companies.
Disclosure of Invention
In order to solve the technical problems, the invention provides carbodiimide modified isocyanate with a long shelf life and a preparation method and application thereof. According to the invention, through the co-catalysis of the phosphorus heterocyclic catalyst and the phosphorus-containing reducing salt, the carbodiimide modified isocyanate is generated by catalyzing the diphenylmethane diisocyanate containing different isomers, and the composition in the carbodiimide modified isocyanate is regulated and controlled by utilizing the activity and steric hindrance difference of the isomers and the selection characteristic of the catalyst, so that the modified isocyanate with long shelf life and low crystallization point is prepared, and the service life of the product is greatly prolonged.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
according to one aspect of the invention, a preparation method of carbodiimide modified isocyanate with long shelf life is provided, which comprises the following steps:
1) Mixing a phosphorus-containing reducing salt and a phosphorus heterocyclic catalyst in an inert low-boiling-point solvent to obtain an activated co-catalyst solution;
2) Adding the co-catalyst solution obtained in step 1) to an isocyanate monomer containing 20-40% by mass of 4,4-diphenylmethane diisocyanate, 25-45% by mass of 2,4-diphenylmethane diisocyanate, 15-55% by mass of 2,2-diphenylmethane diisocyanate; the addition amount of the co-catalyst solution is 0.0003-0.002% of the mass of the isocyanate monomer based on the mass of the phosphorus heterocyclic catalyst;
3) Removing the inert low-boiling-point solvent in the reaction liquid obtained in the step 2), heating to 90-120 ℃, preferably 90-95 ℃, and reacting until the NCO content of the system is 29-30%; cooling to 70-80 ℃, curing at constant temperature for 2-4h, and terminating the reaction to obtain the long-shelf-life carbodiimide modified isocyanate.
Different from the traditional carbodiimide modified product, the invention selects isocyanate with high content of 2,4-MDI and 2,2-MDI isomer as reaction raw materials to improve the storage stability of the product, but the reaction activity of the diphenylmethane diisocyanate with the composition is low, even if a high-efficiency catalyst is used, the reaction rate is still slow at the conventional reaction temperature of 90-120 ℃, and the content of dimer can be obviously increased along with the extension of the reaction time, thus being not beneficial to solving the technical problem provided by the invention; however, if the reaction temperature is increased to increase the reaction rate, the formation rate of the dimer is also high in the reaction process, the conversion rate of the carbodiimide is low, and the dimer quickly reaches the saturation point and is separated out as a solid in the long-term storage process of the modified isocyanate, so that the product quality is influenced.
Aiming at the problems, the invention considers and optimizes the catalyst system, and utilizes the reducing salt containing phosphorus to activate the main catalyst of the phosphacycle in a proper solvent to improve the reaction activity. The introduction of the co-catalysis system can quickly carry out catalytic reaction at a lower temperature, and dimers formed in the reaction process are reduced, so that the shelf life of the prepared modified isocyanate is greatly prolonged, and the crystallization point is lower.
In addition, a carbodiimide structure formed by the 2-position NCO group is more stable than a carbodiimide structure formed by the 4-position NCO group, the steric hindrance is larger, part of carbodiimide in the modified isocyanate can continuously react with the NCO group to form uretonimine, but the possibility of forming an oligomer by the continuous reaction of the uretonimine is reduced, so that the proportion of the carbodiimide and the uretonimine in the product is increased, when the modified isocyanate is applied to an adhesive, the viscosity of a prepolymer is reduced, the pot life is prolonged, and because the mobility of macromolecules is improved, the low-temperature mechanical property is improved, and the low-temperature resistance is excellent.
In a preferred embodiment of the present invention, the phospholane catalyst is one or more of 1-methyl-3-phosphole-1-oxide, 1-methyl-1-oxyphosphole, 3-methyl-1-phenyl-3-phosphole, 2-methyl-2, 5-dioxo-1, 2-oxyphosphole;
preferably, the phosphorus-containing reducing salt is one or more of sodium hypophosphite, zinc phosphite, sodium phosphite, ammonium phosphite and potassium phosphite.
In a preferred embodiment of the invention, the mass ratio of the phosphorus-containing reducing salt to the phosphorus heterocyclic catalyst is (2-10): 1, preferably (3-5): 1.
In a preferred embodiment of the present invention, in step 1), the catalyst mixing and activating conditions are as follows: heating to 55-60 deg.C under 0.2-0.3Mpa, and reacting for 3-4h.
In a preferred embodiment of the present invention, in step 1), the inert low boiling point solvent is acetone.
In a preferred embodiment of the present invention, the isocyanate monomers comprise 30-40%4, 4-diphenylmethane diisocyanate, 35-45%2, 4-diphenylmethane diisocyanate, 20-25%2, 2-diphenylmethane diisocyanate.
In a preferred embodiment of the present invention, the inert low boiling point solvent is removed in step 3) by: heating the reaction solution to 60-65 ℃, and stirring for 1-3h at constant temperature.
In a preferred embodiment of the present invention, in step 3), the terminating reaction is performed by adding a terminating agent, preferably one or more of trifluoromethanesulfonic anhydride, ethyl trifluoromethanesulfonate, propyl trifluoromethanesulfonate, phenyl trifluoromethanesulfonate, adipoyl chloride and benzoyl chloride, to the reaction solution;
preferably, the amount of the terminator is 0.001 to 0.01% by mass of the isocyanate monomer.
According to a second aspect of the present invention there is also provided a long shelf life carbodiimide-modified isocyanate obtained according to the process as hereinbefore described. The storage shelf life of the carbodiimide modified isocyanate is obviously prolonged, and the carbodiimide modified isocyanate is not easy to crystallize when stored at low temperature.
According to a third aspect of the invention, the application of the long-shelf-life carbodiimide modified isocyanate prepared by the method in the preparation of the adhesive is also provided. The adhesive prepared by the modified isocyanate provided by the invention also has the characteristics of low sizing viscosity and excellent low temperature resistance.
The carbodiimide modified isocyanate prepared by the invention has the advantages of prolonged product shelf life, low crystallization temperature, improvement of product storage and use conditions and reduction of product use limitation. In addition, the adhesive prepared by the carbodiimide modified isocyanate has low construction viscosity and excellent low temperature resistance.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be merely illustrative of the invention and not limiting of its scope.
The raw materials and reagents used in the following embodiments of the present invention are commercially available through conventional methods unless otherwise specified.
1-methyl-3-phosphole-1-oxide, available from Shanghai-derived leaf Biotechnology, inc., 99%;
1-methyl-1-oxaphosphole, available from Beijing Wakay Biotech, inc., 99%;
3-methyl-1-phenyl-3-phosphole, available from michelin, 99.5%;
2-methyl-2, 5-dioxo-1, 2-oxaphospholane, available from Honghu Yitai science and technology, inc., 99%;
sodium hypophosphite, available from 99% of Kjeldahl chemical, AR;
sodium phosphite, potassium phosphite, zinc phosphite, ammonium phosphite were purchased from mcelin and purity: >99.5%, AR;
in addition, the MDI with different isomer compositions in each example and comparative example was prepared from Wanhua chemical MDI-100 (containing 4,4-MDI,99.5%;2,4-MDI, 0.5%), MDI-50 (containing 4,4-MDI,49%;2,4-MDI, 51%) and MDI-6001 (containing 4,4-MDI,15%;2,4-MDI,55%;2,2-MDI, 30%).
[ example 1 ]
Adding 450g of acetone and 40g of ammonium phosphite into a 1L glass container, stirring to completely dissolve, transferring to a 1L reaction kettle, continuously adding 10g of 3-methyl-1-phenyl-3-phosphole, sealing the reaction kettle, replacing the reaction kettle with nitrogen for three times, pressurizing to 0.2Mpa, heating to 60 ℃ for constant-temperature reaction for 3 hours, cooling the reaction kettle, releasing the pressure to normal pressure after the temperature is 25 ℃, transferring liquid in the reaction kettle to a dry 1L aluminum bottle, and sealing and storing with nitrogen to obtain an activated co-catalyst solution.
Adding 1000g of MDI (the components are 35% of 4,4-MDI,45% of 2,4-MDI and 20% of 2, 2-MDI) and 0.25g of the above co-catalyst solution into a 2L reaction kettle, heating to 60 ℃, stirring at constant temperature for 2h, removing acetone, then continuously heating to 90 ℃ for reaction until the NCO value of the system is 29%, using for 4.5h, then cooling to 70 ℃, curing at constant temperature for 4h, then adding 0.1g of trifluoromethanesulfonic anhydride, stirring for 1h, cooling to 45 ℃, discharging the liquid in the reaction kettle to obtain carbodiimide modified isocyanate, continuously charging nitrogen in the reaction kettle in the reaction process, and controlling the pressure of the reaction kettle to be less than or equal to 2kPa.
[ example 2 ]
Adding 450g of acetone and 44.5g of zinc phosphite into a 1L glass container, stirring to completely dissolve, transferring to a 1L reaction kettle, continuously adding 5.5g of 1-methyl-1-oxyphospholene, sealing the reaction kettle, replacing the reaction kettle with nitrogen for three times, pressurizing to 0.3Mpa, heating to 55 ℃, carrying out constant temperature treatment for 4 hours, then starting to cool the reaction kettle, releasing the pressure to normal pressure after the temperature is 30 ℃, transferring the liquid in the reaction kettle to a dry 1L aluminum bottle, and storing in a nitrogen sealing manner to obtain the activated co-catalyst solution.
Adding 1000g of MDI (the components are 40% of 4,4-MDI,40% of 2,4-MDI and 20% of 2, 2-MDI) into a 2L reaction kettle, adding 0.45g of the above cocatalyst solution, heating to 65 ℃, stirring for 1h at constant temperature, continuing heating to 95 ℃ for reaction until the NCO value of the system is 29.0%, using for 6h, cooling to 80 ℃, curing at constant temperature for 2h, adding 0.05g of ethyl trifluoromethanesulfonate, stirring for 0.5h, cooling to 50 ℃, discharging the liquid from the reaction kettle to obtain carbodiimide modified isocyanate, continuously filling nitrogen into the reaction kettle in the reaction process, and controlling the pressure of the reaction kettle to be less than or equal to 2kPa.
[ example 3 ]
Adding 450g of acetone and 40g of sodium phosphite into a 1L glass container, stirring to completely dissolve, transferring to a 1L reaction kettle, continuously adding 10g of 1-methyl-3-phosphole-1-oxygen, sealing the reaction kettle, replacing the reaction kettle with nitrogen for three times, pressurizing to 0.2Mpa, heating to 56 ℃, carrying out constant temperature treatment for 3.5 hours, cooling the reaction kettle to 28 ℃, discharging the pressure to normal pressure, transferring the liquid in the reaction kettle to a dry 1L aluminum bottle, and storing in a nitrogen sealing manner to obtain an activated cocatalyst solution.
Adding 1000g of MDI (32% of 4,4-MDI,45% of 2,4-MDI and 23% of 2, 2-MDI) into a 2L reaction kettle, adding 0.5g of the above co-catalyst solution, heating to 62 ℃, stirring for 2 hours at constant temperature, continuously heating to 100 ℃ for reaction until the NCO value of the system is 29.0%, using for 6.5 hours, then cooling to 75 ℃, curing for 2 hours at constant temperature, adding 0.1g of propyl trifluoromethanesulfonate, stirring for 0.5 hour, cooling to 45 ℃, discharging the liquid from the reaction kettle to obtain the carbodiimide modified isocyanate, continuously filling nitrogen into the reaction kettle in the reaction process, and controlling the pressure of the reaction kettle to be less than or equal to 2kPa.
[ example 4 ]
Adding 450g of acetone and 33.3g of potassium phosphite into a 1L glass container, stirring to completely dissolve, transferring to a 1L reaction kettle, continuously adding 16.7g of 1-methyl-1-oxyphosphole, sealing the reaction kettle, replacing the reaction kettle with nitrogen for three times, pressurizing to 0.25Mpa, heating to 60 ℃, carrying out constant temperature treatment for 3 hours, cooling the reaction kettle to 25-30 ℃, discharging the pressure to normal pressure, transferring the liquid in the reaction kettle to a dried 1L aluminum bottle, and storing in a nitrogen sealing manner to obtain the activated co-catalyst solution.
Adding 1000g of MDI (the components are 40% of 4,4-MDI,35% of 2,4-MDI and 25% of 2, 2-MDI) into a 2L reaction kettle, adding 0.6g of the above cocatalyst solution, heating to 65 ℃, stirring for 2 hours at constant temperature, continuing heating to 105 ℃ for reaction until the NCO value of the system is 29.0%, using for 4.5 hours, then cooling to 70 ℃, curing for 3 hours at constant temperature, adding 0.01g of phenyl trifluoromethanesulfonate, stirring for 0.5 hour, cooling to 45 ℃, discharging the liquid from the reaction kettle to obtain carbodiimide modified isocyanate, continuously filling nitrogen into the reaction kettle in the reaction process, and controlling the pressure of the reaction kettle to be less than or equal to 2kPa.
[ example 5 ]
Adding 450g of acetone and 40g of sodium hypophosphite into a 1L glass container, stirring to completely dissolve, transferring to a 1L reaction kettle, continuously adding 10g of 2-methyl-2, 5-dioxo-1, 2-oxyphospholane, sealing the reaction kettle, replacing the reaction kettle with nitrogen for three times, pressurizing to 0.3Mpa, heating to 60 ℃, carrying out constant temperature treatment for 3 hours, cooling the reaction kettle to 25 ℃, discharging the pressure to normal pressure, transferring the liquid in the reaction kettle to a dry 1L aluminum bottle, and storing in a nitrogen sealing manner to obtain an activated cocatalyst solution.
Adding 1000g of MDI (the components are 35 percent of 4,4-MDI,42 percent of 2,4-MDI and 23 percent of 2, 2-MDI) into a 2L reaction kettle, adding 0.15g of the above co-catalyst solution, heating to 65 ℃, stirring for 2 hours at constant temperature, continuing heating to 115 ℃ for reaction until the NCO value of the system is 29.0 percent, using for 3.5 hours, then cooling to 80 ℃, curing for 3 hours at constant temperature, adding 0.03g of adipoyl chloride, stirring for 0.5 hour, cooling to 45 ℃, discharging liquid from the reaction kettle to obtain carbodiimide modified isocyanate, continuously filling nitrogen into the reaction kettle in the reaction process, and controlling the pressure of the reaction kettle to be less than or equal to 2kPa.
[ example 6 ]
Adding 450g of acetone and 45.45g of ammonium phosphite into a 1L glass container, stirring to completely dissolve, transferring to a 1L reaction kettle, continuously adding 4.55g of 3-methyl-1-phenyl-3-phosphole, sealing the reaction kettle, replacing the reaction kettle with nitrogen for three times, pressurizing to 0.2Mpa, heating to 55 ℃, carrying out constant temperature treatment for 4 hours, cooling the reaction kettle to 30 ℃, releasing the pressure to normal pressure, transferring the liquid in the reaction kettle to a dry 1L aluminum bottle, and storing in a nitrogen sealing manner to obtain an activated co-catalyst solution.
Adding 1000g of MDI (consisting of 40% of 4,4-MDI,40% of 2,4-MDI and 20% of 2, 2-MDI) into a 2L reaction kettle, adding 0.55g of the above co-catalyst solution, heating to 60 ℃, stirring for 2 hours at constant temperature, continuing heating to 120 ℃ for reaction until the NCO value of the system is 29.0%, using for 3 hours, then cooling to 80 ℃, curing at constant temperature for 3 hours, adding 0.03g of adipoyl chloride, stirring for 0.5 hour, cooling to 50 ℃, discharging liquid from the reaction kettle to obtain carbodiimide modified isocyanate, continuously charging nitrogen into the reaction kettle in the reaction process, and controlling the pressure of the reaction kettle to be less than or equal to 2kPa.
Comparative example 1
A carbodiimide-modified isocyanate was prepared in substantially the same manner as in example 1, except that the solution of the cocatalyst added in the modification reaction was replaced with 0.005g of 3-methyl-1-phenyl-3-phospholene. In this comparative example, 14 hours was used when the reaction time reached 29.0% NCO.
Comparative example 2
A carbodiimide-modified isocyanate was prepared in substantially the same manner as in example 1 except that 1000g of MDI (composition: 35% of 4,4-MDI,45% of 2,4-MDI,20% of 2, 2-MDI) as the modified reaction material was replaced with 1000g of MDI-100 (containing 4,4-MDI,99.5%;2,4-MDI, 0.5%). In this comparative example, 3 hours was used when the reaction time reached 29.0% NCO.
Comparative example 3
A carbodiimide-modified isocyanate was prepared in substantially the same manner as in example 1, except that the solution of the cocatalyst added in the modification reaction was replaced with 0.005g of 3-methyl-1-phenyl-3-phospholene; at the same time, 1000g of MDI (composition of 35% of 4,4-MDI,45% of 2,4-MDI,20% of 2, 2-MDI) as the raw material for the modification reaction was replaced by 1000g of MDI-100 (comprising 4,4-MDI,99.5%;2,4-MDI, 0.5%). In this comparative example, 5.5h was used when the reaction was carried out to a system NCO value of 29.0%.
Comparative example 4
A carbodiimide-modified isocyanate was prepared in substantially the same manner as in example 1, except that the solution of the cocatalyst added in the modification reaction was replaced with 0.005g of 3-methyl-1-phenyl-3-phosphole and 0.02g of ammonium phosphite. In this comparative example, 12 hours was used when the reaction time reached 29.0% NCO.
[ application example ]
Different adhesives were prepared by using carbodiimide-modified isocyanates prepared in each example and comparative example as raw materials according to the following methods:
60g of polyoxypropylene glycol (molecular weight 2000) is dehydrated for 2h under vacuum at 20 ℃,40 g of carbodiimide modified isocyanate is added after the temperature is reduced to 80 ℃, and the polymerization is carried out for 2h, thus obtaining the component B of the bi-component polyurethane adhesive. 70g of polyoxypropylene diol (molecular weight 1000), 25g of 1, 4-butanediol, 5g of trimethylolpropane and 0.15g of dibutyltin dilaurate are added into a three-necked bottle, stirred uniformly, heated to 80 ℃ and subjected to vacuum dehydration for 4 hours to obtain the component A. And (2) uniformly mixing the components A and B according to the mass ratio of A: B = 1.2 at the normal temperature of 25 ℃ to obtain the adhesive.
Performance test
(1) The carbodiimide modified isocyanate prepared in each example and each comparative example was subjected to a shelf life test at 35 ℃ and the time taken for solid precipitation was recorded, and the test results are shown in table 1;
(2) The carbodiimide-modified isocyanates obtained in the examples and comparative examples were subjected to low-temperature crystallization tests at 5 ℃ and at-5 ℃ respectively, and the time at which low-temperature crystallization occurred was recorded, with the test results shown in Table 2;
(3) Viscosity tests were performed on the adhesive component B prepared in the application example at normal temperature and low temperature (-20 ℃), respectively, and the test results are shown in table 3;
(4) The adhesives prepared in the application examples were respectively sized and cured for 48 hours, and the mechanical properties of the adhesive samples at normal temperature and-20 ℃ were tested, with the test results shown in Table 3.
TABLE 1 storage shelf life test of carbodiimide-modified isocyanates
TABLE 2 Low temperature crystallization test of carbodiimide modified isocyanates
TABLE 3 viscosity and sizing Performance testing of adhesive component B
From the above test results it can be seen that:
(1) The carbodiimide modified isocyanate prepared by the method can obviously shorten the reaction time of low-activity 2,4-MDI and 2,2-MDI, thereby reducing the generation of dimer and prolonging the shelf life of the product.
(2) The carbodiimide modified isocyanate prepared by the embodiments of the invention has excellent storage stability at 35 ℃, has a maximum shelf life of 720 days, has improved product storage and use conditions, and reduces product use limitation.
(3) The carbodiimide modified isocyanate prepared by the embodiments of the invention can keep not crystallizing within three months under the storage condition of-5 ℃.
(4) The adhesive prepared from the carbodiimide modified isocyanate provided by the invention has lower viscosity and excellent low temperature resistance.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for a person skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be considered as the protection scope of the present invention.
Claims (10)
1. A preparation method of carbodiimide modified isocyanate with long shelf life is characterized by comprising the following steps:
1) Mixing a phosphorus-containing reducing salt and a phosphorus heterocyclic catalyst in an inert low-boiling point solvent to obtain an activated co-catalyst solution;
2) Adding the co-catalyst solution obtained in step 1) to an isocyanate monomer containing 20-40% by mass of 4,4-diphenylmethane diisocyanate, 25-45% by mass of 2,4-diphenylmethane diisocyanate, 15-55% by mass of 2,2-diphenylmethane diisocyanate; the addition amount of the co-catalyst solution is 0.0003-0.002% of the mass of the isocyanate monomer based on the mass of the phosphorus heterocyclic catalyst;
3) Removing the inert low-boiling-point solvent in the reaction liquid obtained in the step 2), heating to 90-120 ℃, preferably 90-95 ℃, and reacting until the NCO content of the system is 29-30%; cooling to 70-80 ℃, curing at constant temperature for 2-4h, and terminating the reaction to obtain the long-shelf-life carbodiimide modified isocyanate.
2. The method for preparing long-life carbodiimide-modified isocyanate according to claim 1, wherein said phosphoheterocyclic catalyst is one or more of 1-methyl-3-phospholene-1-oxygen, 1-methyl-1-oxyphospholene, 3-methyl-1-phenyl-3-phospholene, 2-methyl-2, 5-dioxa-1, 2-oxyphospholane;
preferably, the phosphorus-containing reducing salt is one or more of sodium hypophosphite, zinc phosphite, sodium phosphite, ammonium phosphite and potassium phosphite.
3. The method for producing a long-life carbodiimide-modified isocyanate according to claim 2, wherein the mass ratio of the phosphorus-containing reducing salt to the phosphorus-containing heterocyclic catalyst is (2-10): 1, preferably (3-5): 1.
4. The method for preparing a carbodiimide-modified isocyanate with a long shelf life according to claim 3, wherein in the step 1), the catalyst mixing and activating conditions are as follows: heating to 55-60 deg.C under 0.2-0.3Mpa, and reacting for 3-4h.
5. The process for producing a long-life carbodiimide-modified isocyanate according to any one of claims 1 to 4, wherein in step 1), said inert low-boiling solvent is acetone.
6. The method for producing a long-life carbodiimide-modified isocyanate according to claim 1, wherein said isocyanate monomer contains 30-40% of 4,4-diphenylmethane diisocyanate, 35-45% of 2,4-diphenylmethane diisocyanate, and 20-25% of 2,2-diphenylmethane diisocyanate.
7. The method for producing a long-life carbodiimide-modified isocyanate according to claim 5, wherein the inert low-boiling solvent is removed in the step 3) by: heating the reaction solution to 60-65 ℃, and stirring for 1-3h at constant temperature.
8. A process for preparing a long-life carbodiimide-modified isocyanate according to any one of claims 1 to 4, wherein in step 3), said reaction is terminated by adding a terminating agent to the reaction mixture, preferably by adding one or more of trifluoromethanesulfonic anhydride, ethyltrifluoromethanesulfonate, propyltrifluoromethanesulfonate, phenyl trifluoromethanesulfonate, adipoyl chloride and benzoyl chloride;
preferably, the amount of the terminator is 0.001 to 0.01% by mass of the isocyanate monomer.
9. A long shelf life carbodiimide modified isocyanate obtainable by a process according to any one of claims 1 to 8.
10. Use of a long shelf life carbodiimide modified isocyanate obtained by a process according to any one of claims 1 to 8 for the preparation of an adhesive.
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| CN115650880A (en) * | 2022-11-03 | 2023-01-31 | 万华化学（宁波）有限公司 | Recycling method of MDI with over-shelf life, method for preparing carbodiimide modified isocyanate from MDI with over-shelf life and product |
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